Reactions of N- and C-alkenylanilines: VIII. Synthesis of functionalized cycloalka[b]indoles from o-(cycloalk-2-en-1-yl)anilines

Article abstract of DOI:10.1134/S1070428007090096

N-Acyl-2-(cyclohex-2-en-1-yl)anilines react with molecular iodine to give the corresponding N-acyl-1-iodo-1,2,3,4,4a,9a-hexahydrocarbazoles which undergo isomerization into 1-R-2a,3,4,5,5a,10a-hexahydro[1,3]oxazolo[5,4,3-j,k]carbazol- 10-ium iodides; no isomerization occurs with N-acetyl-3-iodo1,2,3,3a,4,8b- hexahydrocyclopenta[b]indole. The reaction of N-p-tolylsulfonyl-3,4,4a,9a- tetrahydrocarbazoles with hydrogen peroxide leads to the formation of a single 1,2-epoxy derivative with trans orientation of the nitrogen-and oxygen-containing rings. N-p-Tolylsulfonyl-1,3a,4,8b-tetrahydrocyclopenta[b] indoles give rise to the corresponding 2,3-epoxy derivatives with both trans and cis orientation of the dihydropyrrole and oxirane fragments. The resulting epoxides undergo trans-opening with formation of N-p-tolylsulfonyl-1-hydroxy-2- methoxy-1,2,3,4,4a,9a-hexahydrocarbazoles and N-p-tolylsulfonyl-3-hydroxy-2- methoxy-1,2,3,3a,4,8b-hexahydrocyclopenta[b]indoles on heating in methanol in the presence of KU-2 cation exchanger. Mutual orientation of the oxirane and nitrogen-containing rings in the epoxides derived from cyclopenta[b]-indoles was proved by X-ray analysis.

Full text of DOI:10.1134/S1070428007090096

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 9, pp. 1310–1321. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © R.R. Gataullin, N.A. Likhacheva, K.Yu. Suponitskii, I.B. Abdrakhmanov, 2007, published in Zhurnal Organicheskoi Khimii, 2007,
Vol. 43, No. 9, pp. 1316–1326.
Reactions of N- and C-Alkenylanilines:
VIII.* Synthesis of Functionalized Cycloalka[b]indoles
from o-(Cycloalk-2-en-1-yl)anilines
R. R. Gataullina, N. A. Likhachevaa, K. Yu. Suponitskiib, and I. B. Abdrakhmanova
a Institute of Organic Chemistry, Ufa Research Center, Russian Academy of Sciences,
pr. Oktyabrya 71, Ufa, 450054 Bashkortostan, Russia
e-mail: chemorg@anrb.ru
b Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, Moscow, Russia
Received September 5, 2006
Abstract—N-Acyl-2-(cyclohex-2-en-1-yl)anilines react with molecular iodine to give the corresponding
N-acyl-1-iodo-1,2,3,4,4a,9a-hexahydrocarbazoles which undergo isomerization into 1-R-2a,3,4,5,5a,10a-hexa-
hydro[1,3]oxazolo[5,4,3-j,k]carbazol-10-ium iodides; no isomerization occurs with N-acetyl-3-iodo-
1,2,3,3a,4,8b-hexahydrocyclopenta[b]indole. The reaction of N-p-tolylsulfonyl-3,4,4a,9a-tetrahydrocarba-
zoles with hydrogen peroxide leads to the formation of a single 1,2-epoxy derivative with trans orientation of
the nitrogen- and oxygen-containing rings. N-p-Tolylsulfonyl-1,3a,4,8b-tetrahydrocyclopenta[b]indoles give
rise to the corresponding 2,3-epoxy derivatives with both trans and cis orientation of the dihydropyrrole and
oxirane fragments. The resulting epoxides undergo trans-opening with formation of N-p-tolylsulfonyl-1-
hydroxy-2-methoxy-1,2,3,4,4a,9a-hexahydrocarbazoles and N-p-tolylsulfonyl-3-hydroxy-2-methoxy-
1,2,3,3a,4,8b-hexahydrocyclopenta[b]indoles on heating in methanol in the presence of KU-2 cation exchanger.
Mutual orientation of the oxirane and nitrogen-containing rings in the epoxides derived from cyclopenta[b]-
indoles was proved by X-ray analysis.
DOI: 10.1134/S1070428007090096
Compounds of the cycloalka[b]indole series exhibit
antitumor [2] and antidepressant [3] activity and are
used in the synthesis of biologically active substances
[4–6]; cycloalka[b]indole fragment is the base structure
of numerous natural alkaloids. Therefore, development
of new methods for their preparation attracts attention
of many researchers [7–16]. However, the number of
publications on the synthesis of difunctional deriva-
tives of these compounds remains so far insignificant.
thesis of difunctional derivatives. As we showed in
[17], 1-halohexahydrocarbazoles II having no protect-
ing group on the nitrogen atom undergo isomerization
into 3-iodotetrahydroquinolines III (Scheme 1). Hexa-
hydrocarbazoles VIIa [18], VIIb [17], and VIIc
obtained by iodocyclization of N-acyl-2-(cyclohex-2-
en-1-yl)anilines VIa–VIc turned out to be involved in
subsequent isomerization in solution on prolonged
storage or on heating for a short time to give fused
tetracyclic compounds VIIIa [18], VIIIb, and VIIIc.
In the present article we report on the results of our
study on the development of procedures for the syn-
thesis of some 1,2-functionalized hexahydrocarbazoles
and 2,3-disubstituted perhydrocyclopenta[b]indoles
from readily accessible o-(cycloalk-2-en-1-yl)anilines.
The key step in the construction of their tricyclic
skeleton is halocyclization of cycloalkenylanilines,
which was extensively studied by us previously. We
found that not all cycloalka[b]indoles available
through the above reaction can be used for the syn-
Anilides VIa–VIc showed a dependence of the
structure of the bromination product on the nature of
the halogenating agent: molecular bromine gave rise
exclusively to (dibromocyclohexyl)anilides [18], while
reactions of anilides VIa–VIc with N-bromosuccin-
imide afforded 7-exocyclization products IV [18]
which were partially hydrolyzed to amines V during
work-up. Hexahydrocyclopenta[b]indole X obtained
by acetylation of compound IX [19] underwent iso-
merization into tetrahydrocyclopenta[b]indole XI in
* For communication VII, see [1].
1310

REACTIONS OF N- AND C-ALKENYLANILINES: VIII.
1311
Scheme 1.
I2, NaHCO3
CCl4
I
CHCl3
N
N
H
H
R
I
R
II
III
NH2
H
H
R
I2, NaHCO3
CH2Cl2
CH2Cl2, >30 days, or
PhH, 80°C, 20 min
I
H
R'COCl
N
N
H
H
O
I–
NHCOR'
R
I
R
R'
O
R
R'
VIa–VIc
VIIa–VIIc
VIIIa–VIIIc
Br
+
NBS, CH2Cl2
Br
VIa–VIc
O
R'
O
R'
NH2
N
IV
R
R
O
V
R′ = Ph, R = H (a), Me (c); R′ = Me, R = H (b).
with trans orientation of the nitrogen-containing and
oxirane rings (an analog of XIIId). In the reactions
with H2O2, the ratio of XIIId–XIIIf and XIVd–XIVf
was about 1:1, presumably due to smaller size of the
oxidant molecule. The reaction mixtures also con-
tained unchanged initial compounds XIId–XIIf. Com-
pounds XIIIe, XIIIf, XIVe, and XIVf were isolated as
individual substances. In the oxidation of XIId, only
epoxide XIVd was isolated (its Rf value was smaller
than that of isomer XIIId). We failed to separate
isomer XIIId from initial compound XIId and cis
isomer XIVd.
a good yield on heating in dimethylformamide at
180°C (Scheme 2).
The most convenient starting compounds for the
synthesis of cycloalka[b]indoles were N-methylsul-
fonyl [20] or N-p-tolylsulfonyl derivatives of o-cyclo-
alkenylanilines [21], which did not undergo isomeriza-
tion. By heating 1-halo-N-p-tolylsulfonyl-1,2,3,4,-
4a,9a-hexahydrocarbazoles or 3-iodo-1,2,3,3a,4,8b-
hexahydrocyclopenta[b]indoles in piperidine we ob-
tained the corresponding tetrahydrocycloalka[b]indoles
XIIa–XIIf [21] (Scheme 3). Oxidation of the latter
with hydrogen peroxide in the presence of formic acid
in an acetonitrile–benzene mixture at 50–60°C gave
stereoisomeric epoxy derivatives XIIIa–XIIIf and
XIVd–XIVf. We previously found [20] that oxidation
of an N-methylsulfonyl analog of XIId with dimethyl-
dioxirane gives 95% of the corresponding epoxide
The structure of the isolated epoxy derivatives was
determined on the basis of their spectral parameters.
Mutual orientation of the oxirane and dihydropyrrole
rings in these compounds was proved by X-ray anal-
ysis of single crystals of XIIIf and XIVf as examples
Scheme 2.
H
H
H
Ac2O, CHCl3, 20°C
DMF, 180°C
N
N
N
I
I
H
H
H
H
Ac
Ac
IX
X, 84%
XI, 70%
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 9 2007

GATAULLIN et al.
1312
Scheme 3.
R'
R'
H
R'
H
H
( )n
( )n
( )n
H2O2, HCOOH, MeCN
PhH, 50–60°C
+
O
O
N
N
N
H
H
H
R
R
R
Ts
XIIa–XIIf
Ts
Ts
XIIIa–XIIIf
XIVd–XIVf
n = 2, R = Me, R′ = H (a), R = MeO, R′= H (b), R = R′ = Me (c); n = 1, R = Me, R′ = H (d), R = MeO, R′ = H (e), R = R′ = Me (f).
(Fig. 1). The five-membered rings in trans isomer
XIIIf are fairly flat; the mean-square deviations of
atoms from the planar structures are 0.055 and
0.031 Å, respectively, for the N4C4aC8aC8bC3a and
C1C2C3C3aC8b rings. In the molecule of cis isomer
XIVf, analogous rings are less planar: the mean-square
deviations are 0.092 and 0.088 Å, respectively, for the
N4C4aC8aC8bC3a and C1C2C3C3aC8b rings. The dihedral
angles between the C1C2C3C3aC8b ring, on the one
hand, and N4C4aC8aC8bC3a and C2C3O1, on the other,
are 65.57(8) and 74.12(10)° for the trans isomer and
67.73(7) and 79.86(10)° for the cis isomer, respec-
tively; it is seen that these angles in both isomers are
fairly similar. The configuration of the p-tolylsulfonyl
group was described by the torsional angles C4aN4S1O2,
C3aN4S1O3, and O2S1C11C12 which were equal to 53.7,
54.3, and 43.6°, respectively, for isomer XIIIf and to
–48.1, 62.3, and 40.2° for XIVf. Thus, the principal
difference between molecules XIIIf and XIVf is the
orientation of the epoxy group (trans or cis).
(a)
C6
C9
C7
C5
C8
C10
C4a
N1
C8a
O2
C12
C11
C1
S1
C8b
C3a
C13
C14
C15
C2
C3
O3
O1
C16
The crystalline structures of both isomers XIIIf and
XIVf lack any specific intermolecular interactions, and
their molecules in crystal are linked through van der
Waals forces; in addition, very weak C–H···O contacts
were revealed, which can be regarded as intermediate
between van der Waals interactions and normal hydro-
gen bonds [XIIIf: C16–H16a ···O2: C16 ···O2 3.291(2),
C17
(b)
C6
C7
C9
H
16a···O2 2.67 Å, ∠CHO 123°; XIVf: C17–H17a ···O2,
C5
C8
C17···O2 3.370(2), H17a···O2 2.46 Å, ∠CHO 155°].
C10
Some similarities were also found between crystal
packings of compounds XIIIf and XIVf. The above
weak C–H···O intermolecular contacts give rise to
chains extended along the crystallographic a axis for
trans isomer XIIIf and b axis for cis isomer XIVf
(Figs. 2, 3). In both structures, the above contacts
involve carbon atoms of the toluene fragment and
similarly arranged oxygen atoms of the sulfonyl group.
Some differences are observed in mutual orientations
of their molecules within the chain and orientations of
the neighboring chains. In the crystalline structure of
XIIIf, molecules in a chain are related to each other
through a plane orthogonal to the c axis, and in the
structure of XIVf, through a second-order symmetry
O2
C4a
C12
C8a
C8b
N1
C13
S1
O1
C11
C14
O3
C2
C17
C3a
C1 C3
C16
C15
Fig. 1. Structures of molecules (a) XIIIf and (b) XIVf
according to the X-ray diffraction data. Non-hydrogen atoms
are shown as thermal ellipsoids with a probability of 50%.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 9 2007

REACTIONS OF N- AND C-ALKENYLANILINES: VIII.
1313
b
a
c
0
b
c
0
a
Fig. 2. A fragment of crystal packing of compound XIIIf.
Fig. 3. A fragment of crystal packing of compound XIVf.
axis. The chain couples shown in Figs. 2 and 3 are re-
lated to each other through the 21 axis which is parallel
to the crystallographic c axis for compound XIIIf and
through translation along the a axis for isomer XIVf.
Analysis of the role of weak interactions in crystal
is fairly complex [22], especially when the only inter-
molecular interactions are van der Waals or weak
C–H···O contacts, as in the crystalline structures of
XIIIf and XIVf. With a view to obtain more detailed
information on their crystal packing, we calculated the
energies of intramolecular interactions in terms of the
atom–atom potential method using NONVPOT pro-
gram [23] with Mirsky’s parameterization [24]. In both
structures, each molecule interacts most strongly with
4–5 neighboring molecules, thus forming a three-
dimensional structure. This means that neither chains
(columns) nor layers where interactions within a chain
(layer) would be considerably stronger than those be-
tween different chains (layers) could be distinguished
in the crystalline structures of XIIIf and XIVf. Ac-
cording to the calculations, the energies of the crystal
packings differ by only 3 kcal/mol and are –26.6 and
–29.6 kcal/mol for XIIIf and XIVf, respectively. The
more energetically favorable structure of XIVf is char-
acterized by slightly tighter packing (see table).
epoxy derivatives, we made an attempt to effect iodo-
cyclization of N-(p-nitrophenylsulfonyl)-2-(2-cyclo-
penten-1-yl)-3,6-dimethylaniline having a bulkier pro-
tecting group. However, we failed to isolate the
expected cyclization product, presumably for steric
reasons. Therefore, we synthesized N-methylsulfonyl-
tetrahydrocyclopenta[b]indole XV with a smaller
N-substituent as compared to tosyl group. Compound
XV was obtained according to Scheme 4 using 2-(cy-
clopent-2-en-1-yl)-3,6-dimethylaniline (XVI) [25] as
starting material.
The oxidation of XV with hydrogen peroxide led
to the formation of a mixture of approximately equal
amounts of isomeric epoxy derivatives XIX and XX.
The reactions of cyclohexene analogs XIIa–XIIc with
H2O2 gave epoxides XIIIa–XIIIc which were separat-
ed from unreacted initial compounds XIIa–XIIc by
column chromatography. The absence of products with
cis orientation of the dihydropyrrole and oxirane rings
was rationalized in terms of steric effect of an “extra”
methylene group, which is well demonstrated by mo-
lecular modeling.
Heating of epoxy derivatives XIIIa and XIIIc in
methanol in the presence of KU-2 cation exchanger
resulted in trans-opening of the oxirane ring with
formation of methoxy alcohols XXIa and XXIc in
good yields (Scheme 5). The use of KU-2 in acetic
In order to elucidate how the size of the protecting
group on the nitrogen atom affects the ratio of isomeric
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 9 2007

GATAULLIN et al.
1314
Scheme 4.
Me
Me
Me
Me
H
MeSO2Cl, pyridine
I2, NaHCO3, CH2Cl2
N
NH2
NHSO2Me
I
H
Me
SO2Me
Me
XVI
XVII
XVIII
Me
H
Me
H
Me
H
H2O2, HCOOH
MeCN, PhH
Piperidine, 120–130°C
O
O
+
N
N
H
SO2Me
N
H
H
Me
Me
Me
SO2Me
SO2Me
XV
XIX
XX
Scheme 5.
R'
H
MeOH, KU-2, 50–55°C
OMe
R'
H
N
H
R
OH
Ts
XXIa, XXIc
O
N
H
H
H
R
Ts
AcOH, H2SO4
R = Me, R' = H
+
XIIIa, XIIIc
OAc
OAc
N
H
Ts
N
H
Me
OH
Me
OAc
Ts
XXII
XXIII
R = Me, R′ = H (a), R = R′ = Me (c).
acid to effect cleavage of XIIIa was unsuccessful. The
reaction of XIIIa with acetic acid in the presence of
sulfuric acid gave monoacetate XXII as a result of
trans-opening of the oxirane ring. In addition, diace-
tate XXIII was isolated; presumably, the latter was
formed via subsequent esterification of monoacetate
XXII. Treatment of compound XIIIf in methanol in
the presence of KU-2 afforded methoxy derivative
XXIV. Under analogous conditions, from epoxides
XIVd and XIVf we obtained the corresponding
methoxy alcohols XXVd and XXVf in good yields
(Scheme 6).
isomeric 2,3-epoxy derivatives with cis and trans
arrangement of the oxirane and nitrogen-containing
rings.
EXPERIMENTAL
The IR spectra were recorded on a UR-20 instru-
1
ment. The H and 13C NMR spectra were measured
on a Bruker AM-300 spectrometer at 300.13 and
75.47 MHz, respectively, using tetramethylsilane as
internal reference. The elemental compositions were
determined on an M-185B CHN Analyzer. Column
chromatography was performed on silica gel LS (40–
100 μm; from Lancaster). Sorbfil plates (Sorbpolimer
Ltd., Krasnodar, Russia) were used for qualitative TLC
analysis; development with iodine vapor.
We can conclude that N-p-tolylsulfonyl-3,4,4a,9a-
tetrahydrocarbazoles react with hydrogen peroxide to
give the corresponding 1,2-epoxy-N-p-tolylsulfonyl-
1,2,3,4,4a,9a-hexahydrocarbazoles with high stereo-
selectivity. N-p-Tolylsulfonyl-1,3a,4,8b-tetrahydro-
cyclopenta[b]indoles give rise to mixtures of stereo-
Single crystals of compounds XIIIf and XIVf were
obtained by slow crystallization from 95% ethanol.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 9 2007

REACTIONS OF N- AND C-ALKENYLANILINES: VIII.
1315
Scheme 6.
Me
Me
H
H
OMe
MeOH, KU-2, 50–55°C
O
N
N
OH
H
H
Me
Me
Ts
Ts
XIIIf
XXIV
R'
R'
H
H
OMe
MeOH, KU-2, 50–55°C
O
N
N
OH
H
H
R
R
Ts
Ts
XIVd, XIVf
XXVd, XXVf
R = Me, R′ = H (d), R = R′ = Me (f).
The X-ray diffraction data were acquired on a SMART
1000 CCD diffractometer [λ(MoKα) 0.71073 Å, graph-
ite monochromator, ω-scanning] at 120 K. The prin-
cipal crystallographic parameters are given in table.
The sets of reflection intensities were processed using
SAINT Plus [26] and SADABS programs [27]. The
structures were solved by the direct method and were
refined by the full-matrix least-squares procedures in
anisotropic approximation for non-hydrogen atoms
(with respect to Fhkl2) using SHELXTL-97 software
package [28]. The positions of hydrogen atoms were
calculated from the geometry considerations and were
refined using the riding model [Uiso(H) = nUeq(C),
where n = 1.5 for methyl carbon atoms, and n = 1.2 for
the other carbon atoms].
N-Benzoyl-1-iodo-8-methyl-1,2,3,4,4a,9a-hexa-
hydrocarbazole (VIIc). A mixture of 0.29 g (1 mmol)
of benzamide VIc, 0.84 g (10 mmol) of NaHCO3, and
0.51 g (2 mmol) of I2 in 20 ml of methylene chloride
was stirred at room temperature until the initial ben-
zamide disappeared. The mixture was diluted with
30 ml of methylene chloride and treated with 10%
aqueous Na2S2O3 (2×20 ml), and the organic phase
was washed with water (2×10 ml), dried over MgSO4,
and evaporated under reduced pressure. Yield 0.4 g
(96%), amorphous material, Rf 0.5 (benzene). 1H NMR
spectrum (CDCl3), δ, ppm: 0.90–1.00 m (6H, CH2),
2.20 s (3H, CH3), 3.70–3.77 m (1H, 4a-H), 3.90 d.d.d
(1H, 1-H, J1 = 4.0, J2 = 9.0, J3 = 13.0 Hz), 5.00–5.03 m
(1H, 9a-H), 7.00–7.05 m (8H, Harom). Found, %:
C 57.13; H 4.43; I 30.02; N 2.98. C20H20INO. Calcu-
lated, %: C 57.57; H 4.83; I 30.41; N 3.36.
pound VIb, 0.25 g (1.2 mmol), was subjected to iodo-
cyclization [20]. After appropriate treatment, product
VIIb was dissolved in 3 ml of benzene, and the solu-
tion was heated for 20 min under reflux. After cooling,
the solvent was separated from the crystalline product
by decanting. Yield 0.31 g (79%), colorless crystals,
1
mp 175°C (from benzene). H NMR spectrum
(CDCl3), δ, ppm: 1.20–2.00 m (6H, CH2), 2.1 s (3H,
CH3), 3.19 d.t (1H, 5a-H, J1 = 6.2, J2 = 10.7 Hz),
4.00 d.d (1H, 10a-H, J1 = 4.8, J2 = 6.4 Hz), 5.11 d.d.d
(1H, 2a-H, J1 = 6.4, J2 = 6.7, J3 = 15.2 Hz), 6.90–
7.20 m (4H, Harom). 13C NMR spectrum (DMSO-d6),
δC, ppm: 21.2, 25.6, 29.0 (CH2); 21.8 (CH3);
41.3 (C5a); 60.5 (C10a); 72.9 (C2a); 109.7, 117.7, 122.9,
127.2, 134.5, 150.5 (Carom); 170.1 (N+=C–O). Found,
%: C 48.97; H 4.44; I 36.82; N 3.76; anionic iodine:
36.12%. C19H18INO. Calculated, %: C 49.28; H 4.73;
I 37.19; N 4.11.
9-Methyl-1-phenyl-2a,3,4,5,5a,10a-hexahydro-
[1,3]oxazolo[5,4,3-jk]carbazol-10-ium iodide
(VIIIc). A mixture of 0.42 g (1 mmol) of compound
VIIc and 3 ml of benzene was heated for 20 min under
reflux. After cooling, the precipitate was filtered off.
Yield 0.37 g (88%), colorless crystals, mp 157–159°C.
IR spectrum, ν, cm–1: 1725, 1475, 1375, 1270, 1115,
1035, 775, 725. UV spectrum (MeCN): λmax 365, λmin.
330 nm. 1H NMR spectrum (DMSO-d6), δ, ppm: 1.20–
2.39 m (6H, CH2), 2.40 s (3H, CH3), 3.70 d.t (1H,
5a-H, J1 = 6.2, J2 = 8.8 Hz), 4.70 d.d (1H, 10a-H, J1 =
4.6, J2 = 6.2 Hz), 5.65 d.d.d (1H, 2a-H, J1 = 4.6, J2 =
4.9, J3 = 9.2 Hz), 7.00–7.60 m (8H, Harom). 13C NMR
spectrum (CDCl3), δC, ppm: 21.6 (CH3); 18.4, 26.6,
26.7 (CH2); 40.6 (C5a); 61.4 (C10a); 70.3 (C2a); 120.9,
1-Methyl-2a,3,4,5,5a,10a-hexahydro[1,3]oxazolo-
[5,4,3-jk]carbazol-10-ium iodide (VIIIb). Com-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 9 2007

GATAULLIN et al.
Crystallographic data for compounds XIIIf and XIVf and parameters of X-ray diffraction experiments
1316
Parameter
VIIIf
IXf
Formula
C20H21NO3S
355.44
C20H21NO3S
355.44
Molecular weight
Color and shape of crystal
Colorless prism
0.30×0.25×0.20
Orthorhombic
Pbca
Colorless prism
0.20×0.15×0.10
Monoclinic
P21/n
Crystal habit, mm
Crystal system
Space group
a, Å
12.4398(9)0
16.3531(11)
17.3960(13)
90
08.7077(6)
14.3510(9)
14.3817(9)
104.24(10)
4
b, Å
c, Å
β, deg
Z
V, Å3
dcalc, mg/m3
8
3538.9(4)
1.334
1741.9(2)
1.355
Absorption coefficient μ, mm–1
0.202
0.205
F(000)
1504
752
Scan range θ, deg
2.34–27.00
18886
2.04–27.00
14990
Total number of reflections
Number of independent reflections
Rint
03821
03755
0.0284
0.0301
Number of refined parameters
Number of reflections with I > 2σ(I)
Completeness of reflection set, %
Goodness of fit
0229
0229
3029
3030
98.9
99.0
1.036
1.005
Divergence factor R1(F)a for reflections with I > 2σ(I)a
Divergence factor wR2(F2)b for all reflections
Residual electron density, max/min, e/Å3
0.0452
0.0420
0.0932
0.0874
0.460/–0.336
0.374/–0.332
a
R1 = Σ|Fo – |Fc||/Σ(Fo).
wR2 = {Σ[w(Fo2 – Fc2)2]/Σ[w(Fo ) ]}1/2
.
b
2 2
128.2, 129.6, 129.7, 129.8, 133.1 (C6, C7, C8, C2′/C6′,
C3′/C5′, C4′); 127.5, 129.2, 137.0, 137.7, 165.7 (C5b, C9,
C9a, C1′, N+=C–O). Found, %: C 57.28; H 3.04;
I 30.02; N 3.05; anionic iodine: 29.98%. C20H20INO.
Calculated, %: C 57.57; H 4.83; I 30.41; N 3.36.
the residue was recrystallized from hexane. Yield
0.83 g (80%), colorless crystals, mp 123–125°C.
1H NMR spectrum (CDCl3), δ, ppm: 1.60–1.80 m (1H,
2-H), 1.90–2.15 m (2H, CH2), 2.45 s (3H, CH3), 2.55–
2.70 m (1H, 2-H), 4.00 t (1H, 8b-H, J = 8.0 Hz), 4.40 d
(1H, 3-H, J = 4.2 Hz), 5.07 d (1H, 3a-H, J = 8.0 Hz),
6.80–7.03 m (4H, Harom). Found, %: C 47.45; H 3.94;
I 38.48; N 4.01. C13H14INO. Calculated, %: C 47.73;
H 4.31; I 38.79; N 4.28.
N-Acetyl-3-iodo-1,2,3,3a,4,8b-hexahydrocyclo-
penta[b]indole (X). Acetic anhydride, 0.27 ml
(4.5 mmol), was added under stirring to a solution of
0.9 g (3.15 mmol) of compound IX [19] in 3 ml of
chloroform, and the mixture was left to stand for 24 h
at room temperature. When the reaction was complete,
the mixture was treated with a 10% solution of
N-Acetyl-1,3a,4,8b-tetrahydrocyclopenta[b]in-
dole (XI). Compound X, 0.33 g (1 mmol), was heated
in dimethylformamide for 4 h at 180°C. When the
NaHCO3 (2×50 ml) and extracted with chloroform reaction was complete, the solvent was distilled off
(2× 50 ml). The organic extracts were dried over
Na2SO4 and evaporated under reduced pressure, and
under reduced pressure, the residue was dissolved in
50 ml of methylene chloride, the solution was washed
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 9 2007

REACTIONS OF N- AND C-ALKENYLANILINES: VIII.
1317
(XIIIc). Yield 0.75 g (68%), colorless crystals,
mp 156–159°C (from EtOH). H NMR spectrum
with water (2×20 ml), dried over Na2SO4, and evap-
orated under reduced pressure, and the residue was
recrystallized from hexane. Yield 0.14 g (70%), color-
1
(C6D6–CCl4), δ, ppm: 1.00–2.00 m (4H, CH2); 1.90 s,
2.15 s, and 2.45 s (3H each, CH3); 2.20 m (1H, 4a-H);
2.70 m (1H, 1-H); 3.05 d (1H, 2-H, J = 3.6 Hz); 4.30 d
(1H, 9a-H, J = 7.7 Hz); 6.65 d (1H, Harom, J = 7.7 Hz);
6.85 d (2H, Harom, J = 8.3 Hz); 7.05–7.15 m (3H,
Harom). 13C NMR spectrum (C6D6–CCl4), δC, ppm:
15.7, 19.9 (C3, C4); 19.3, 20.1, 20.8 (CH3); 38.0 (C4a);
51.0 (C2); 53.6 (C1); 60.4 (C9a); 128.5, 128.8, 129.2,
130.9 (C6, C7, C2′/C6′, C3′/C5′); 130.2, 131.2, 135.4,
135.5, 142.2, 143.3 (C4b, C5, C8, C8a, C1′, C4′). Found,
%: C 68.63; H 6.15; N 3.89; S 8.55. C21H23NO3S.
Calculated, %: C 68.27; H 6.27; N 3.79; S 8.68.
1
less crystals, mp 105–108°C. H NMR spectrum
(CDCl3), δ, ppm: 2.30 s (3H, CH3), 2.60 d.t (1H, 1-HA,
J1 = 1.8, J2 = 17.1 Hz), 3.00 d.d.d.t (1H, 1-HB, J1 = 1.8,
J2 = 2.7, J3 = 8.3, J4 = 17.1 Hz), 4.10 t.d (1H, 8b-H,
J1 = 1.8, J2 = 8.3 Hz), 5.30 d.q (1H, 3a-H, J1 = 1.8, J2 =
8.3 Hz), 5.90 d.t (1H, 2-H, J1 = 1.8, J2 = 6.0 Hz),
6.00 d.t (1H, 3-H, J1 = 1.8, J2 = 6.0 Hz), 7.00–7.20 m
(3H, Harom), 8.10 d (1H, 5-H, J = 8.0 Hz). Found, %:
C 78.05; H 6.26; N 6.81. C13H13NO. Calculated, %:
C 78.36; H 6.58; N 7.03.
Epoxy derivatives XIIIa–XIIIc and XIVd–XIVf.
A solution of 3 mmol of compound XIIa–XIIf in
80 ml of benzene was added to a mixture of 6 ml of
formic acid and 5 ml of 33% hydrogen peroxide,
135 ml of acetonitrile was then added, and the mixture
was heated for 16–17 h at 50–60°C. After cooling to
room temperature, the mixture was washed with 10%
aqueous NaHCO3 until carbon dioxide no longer
evolved and with water (3×50 ml). The organic phase
was dried over MgSO4 and evaporated under reduced
pressure, and the residue was recrystallized from
ethanol (compounds XIIIa–XIIIc) or subjected to
chromatography on silica gel using benzene as eluent
to isolate epoxides XIIId–XIIIf and XIVd–XIVf.
(1S,2R,4aS,9aR)-2,3-Epoxy-8-methyl-9-p-tolyl-
sulfonyl-1,2,3,4,4a,9a-hexahydrocarbazole (XIIIa).
Yield 0.89 g (84%), colorless crystals, mp 175–177°C
(from EtOH). 1H NMR spectrum (C6D6–CCl4), δ, ppm:
1.05–1.65 m (4H, CH2), 2.15 m (4H, 4a-H, CH3),
2.51 s (3H, CH3), 2.67 m (1H, 2-H), 3.02 d (1H, 1-H,
J = 3.5 Hz), 4.39 d (1H, 9a-H, J = 8.0 Hz), 6.50 d (1H,
Harom, J = 7.2 Hz), 6.82–7.25 m (6H, Harom). Found, %:
C 67.63; H 6.02; N 3.89; S 8.95. C20H21NO3S. Calcu-
lated, %: C 67.58; H 5.95; N 3.95; S 9.02.
(2R,3S,3aR,8bS)-2,3-Epoxy-5-methoxy-4-p-tolyl-
sulfonyl-1,2,3,3a,4,8b-hexahydrocyclopenta[b]in-
dole (XIIId). Yield 0.27 g (26%), colorless crystals,
1
mp 119–121°C (from EtOH). H NMR spectrum
(C6D6–CCl4), δ, ppm: 1.60 d.d.d (1H, 1-HA, J1 = 2.2,
J2 = 4.2, 2J = 14.4 Hz), 2.28 s (3H, CH3), 2.32 d.d (1H,
2
1-HB, J1 = 8.3, J = 14.4 Hz), 3.26 t (1H, 2-H, J =
2.2 Hz), 3.40 d.t (1H, 8b-H, J1 = 4.2, J2 = 8.3 Hz),
3.49 s (3H, CH3), 3.72 d (1H, 3-H, J = 2.2 Hz), 4.97 d
(1H, 3a-H, J = 8.3 Hz), 6.50 d (1H, Harom, J = 7.5 Hz),
6.54 d (1H, Harom, J = 8.3 Hz), 6.83 t (1H, 7-H, J =
7.9 Hz), 7.05 d (2H, Harom, J = 8.3 Hz), 7.60 d (2H,
Harom, J = 8.3 Hz). Found, %: C 63.63; H 5.25; N 3.89;
S 8.95. C19H19NO4S. Calculated, %: C 63.85; H 5.36;
N 3.92; S 8.97.
(2R,3S,3aR,8bS)-2,3-Epoxy-5,8-dimethyl-4-p-tol-
ylsulfonyl-1,2,3,3a,4,8b-hexahydrocyclopenta[b]in-
dole (XIIIf). Yield 0.38 g (36%), colorless crystals,
1
mp 134–136°C (from EtOH). H NMR spectrum
(C6D6–CCl4), δ, ppm: 1.45 d.t (1H, 1-HA, J1 = 2.5, 2J =
14.3 Hz), 1.95 s (3H, CH3), 2.20 d.d (1H, 1-HB, J1 =
8.7, 2J = 14.3 Hz), 2.26 s (3H, CH3), 2.60 s (3H, CH3),
2.90 d.t (1H, 8b-H, J1 = 2.5, J2 = 7.7 Hz), 3.15 m (1H,
3-H), 3.70 m (1H, 2-H), 4.45 d (1H, 3a-H, J = 7.7 Hz),
6.75 d (1H, Harom, J = 7.6 Hz), 6.90–7.00 m (3H,
(1S,2R,4aS,9aR)-2,3-Epoxy-8-methoxy-9-p-tolyl-
sulfonyl-1,2,3,4,4a,9a-hexahydrocarbazole (XIIIb).
Yield 0.56 g (50%), colorless crystals, mp 159–161°C
(from EtOH). 1H NMR spectrum (C6D6–CCl4), δ, ppm:
1.10–1.75 m (4H, CH2), 2.20 s (3H, CH3), 2.70 m (2H,
2-H, 4a-H), 2.90 d (1H, 1-H, J = 3.6 Hz), 3.67 s (3H,
OCH3), 4.62 d (1H, 9a-H, J = 7.1 Hz), 6.40 d (1H,
Harom, J = 7.4 Hz), 6.63 d (1H, Harom, J = 7.5 Hz), 6.90 m
(3H, Harom), 7.45 d (2H, Harom, J = 8.2 Hz). Found, %:
C 64.83; H 5.52; N 3.80; S 8.75. C20H21NO4S. Cal-
culated, %: C 64.67; H 5.70; N 3.77; S 8.63.
H
arom), 7.15 d (2H, Harom, J = 8.0 Hz). Found, %:
C 67.53; H 6.02; N 3.99; S 8.95. C20H21NO3S. Cal-
culated, %: C 67.58; H 5.95; N 3.95; S 9.02.
(2S,3R,3aS,8bS)-2,3-Epoxy-5-methyl-4-p-tolyl-
sulfonyl-1,2,3,3a,4,8b-hexahydrocyclopenta[b]in-
dole (XIVd). Yield 0.3 g (29%), colorless crystals,
1
mp 182–184°C (from EtOH). H NMR spectrum
(C6D6–CCl4), δ, ppm: 1.70 d.d.d (1H, 1-HA, J1 = 2.0,
J2 = 9.0, J3 = 14.5 Hz), 1.93 d (1H, 1-HB, J = 14.5 Hz),
2.22 s (3H, CH3), 2.55 s (3H, CH3), 3.13 m (1H, 3-H),
3.58 t (1H, 8b-H), 4.47 d.d (1H, 3a-H, J1 = 2.0, J2 =
(1S,2R,4aS,9aR)-2,3-Epoxy-5,8-dimethyl-9-p-tol-
ylsulfonyl-1,2,3,4,4a,9a-hexahydrocarbazole
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 9 2007

GATAULLIN et al.
1318
8.1 Hz), 6.60 d (1H, Harom, J = 7.7 Hz), 6.70–7.05 m
(3H, Harom), 7.20 d (2H, Harom, J = 8.3 Hz). Found, %:
C 66.92; H 5.62; N 4.15; S 9.48. C19H19NO3S. Cal-
culated, %: C 66.84; H 5.61; N 4.10; S 9.39.
stirred until initial compound XVII disappeared,
washed with an aqueous solution of Na2S2O3 and water
(20 ml), dried over MgSO4, and evaporated to obtain
10.58 g (98%) of compound XVIII as an oily sub-
stance, Rf 0.69 (C6H6–EtOAc, 9:1). 1H NMR spectrum
(acetone-d6), δ, ppm: 1.64–1.78 m (1H, 1-HA), 1.98–
2.11 m (2H, 1-HB, 2-HA), 2.42–2.52 m (1H, 2-HB),
2.30 s (3H, CH3), 2.40 s (3H, CH3), 2.97 s (3H, CH3),
4.01–4.14 m (2H, 8b-H, 3-H), 5.04 d.d (1H, 3a-H, J1 =
6.8, J2 = 8.4 Hz), 6.99 d (1H, 7-H, J = 7.7 Hz), 7.40 d
(1H, 6-H, J = 7.7 Hz).
(2S,3R,3aS,8bS)-2,3-Epoxy-5-methoxy-4-p-tolyl-
sulfonyl-1,2,3,3a,4,8b-cyclopenta[b]indole (XIVe).
Yield 0.33 g (31%), colorless crystals, mp 172–174°C
(from EtOH). 1H NMR spectrum (C6D6–CCl4), δ, ppm:
2
1.99 d (1H, 1-HA, J1 = 9.3, J = 12.8 Hz), 2.12 d (1H,
2
1-HB, J = 12.8 Hz), 2.30 s (3H, CH3), 3.29 m (1H,
3-H), 3.45–3.52 m (4H, OCH3, 8b-H), 3.62 m (1H,
2-H), 5.00 d (1H, 3a-H, J = 8.8 Hz), 6.40 d (1H, Harom
,
Compound XVIII was dissolved in 80 ml of piper-
idine, and the mixture was heated for 8 h at the boiling
point. Piperidine was distilled off under reduced pres-
sure, the residue was dissolved in 200 ml of methylene
chloride, the solution was washed with water (3×
30 ml) and dried over MgSO4, the solvent was distilled
off under reduced pressure, and the residue was recrys-
tallized from ethanol. Yield of XV 7.1 g (60% on the
initial compound XVI), colorless crystals, mp 117–
J = 7.7 Hz), 6.54 d (1H, Harom, J = 8.0 Hz), 6.80 d.d
(1H, Harom, J1 = 7.7, J2 = 8.0 Hz), 7.05 d (2H, Harom, J =
7.85 Hz), 7.60 d (2H, Harom, J = 7.8 Hz). Found, %:
C 63.75; H 5.45; N 3.99; S 8.95. C19H19NO4S. Calcu-
lated, %: C 63.85; H 5.36; N 3.92; S 8.97.
(2S,3R,3aR,8bS)-2,3-Epoxy-5,8-dimethyl-4-p-tol-
ylsulfonyl-1,2,3,3a,4,8b-hexahydrocyclopenta[b]in-
dole (XIVf). Yield 0.39 g (37%), colorless crystals,
1
1
119°C (from EtOH). H NMR spectrum (CDCl3), δ,
mp 123–125°C (from EtOH). H NMR spectrum
ppm: 2.18 s (3H, CH3), 2.21 s (3H, CH3), 2.38 d.q
(C6D6–CCl4), δ, ppm: 1.69 d.d.d (1H, 1-HA, J1 = 1.0,
2
2
(1H, 1-HA, J1 = 2.2, J = 18.4 Hz), 2.70 s (3H, CH3),
J2 = 8.0, J = 13.5 Hz), 1.90 s (3H, CH3), 2.03 d (1H,
2.79 d.d.q (1H, 1-HB, J1 = 2.2, J2 = 8.0, 2J = 18.4 Hz),
4.18 d.t (1H, 8b-H, J1 = 7.7, J2 = 8.0 Hz), 5.35 d.q (1H,
3a-H, J1 = 2.2, J2 = 7.7 Hz), 5.57 m (1H, 2-H), 5.67 m
(1H, 3-H), 6.80 d (1H, Harom, J = 7.8 Hz), 6.90 d (1H,
Harom, J = 7.8 Hz). Found, %: C 63.63; H 6.02; N 5.19;
S 12.05. C14H17NO2S. Calculated, %: C 63.85; H 6.51;
N 5.31; S 12.18.
2
1-HB, J = 13.5 Hz), 2.20 s (3H, CH3), 2.50 s (3H,
CH3), 2.63 t (1H, 8b-H, J = 8.0 Hz), 3.15 m (1H, 3-H),
3.55 m (1H, 2-H), 4.50 d.d (1H, 3a-H, J1 = 2.0, J2 =
8.0 Hz), 6.69 d (1H, Harom, J = 7.7 Hz), 6.80–6.95 m
(3H, Harom), 7.11 d (2H, Harom, J = 7.9 Hz). Found, %:
C 67.61; H 6.00; N 3.99; S 9.05. C20H21NO3S. Calcu-
lated, %: C 67.58; H 5.95; N 3.95; S 9.02.
Epoxidation of N-methylsulfonyl derivative XV.
A solution of 0.79 g (3 mmol) of compound XV in
80 ml of benzene was added to a mixture of 6 ml of
formic acid and 5 ml of 33% hydrogen peroxide,
135 ml of acetonitrile was then added, and the mixture
was heated for 17 h at 50–60°C. After cooling to room
temperature, the mixture was washed with a 10%
aqueous solution of NaHCO3 until carbon dioxide no
longer evolved and with water (3×50 ml). The organic
phase was separated, dried over MgSO4, and evapo-
rated under reduced pressure, and the residue, a mix-
ture of cis and trans isomers XIV and XV, was sep-
arated by chromatography on silica gel using benzene
as eluent.
4-Methylsulfonyl-5,8-dimethyl-1,3a,4,8b-tetra-
hydrocyclopenta[b]indole (XV). Methanesulfonyl
chloride, 5.15 g (45 mmol), was added to a solution of
5.61 g (30 mmol) of 2-(cyclopent-2-en-1-yl)-3,6-di-
methylaniline (XVI) [25] in 15 ml of pyridine. After
24 h, the mixture was diluted with 200 ml of methyl-
ene chloride and washed with 5% hydrochloric acid to
remove pyridine and water (25 ml), and the organic
phase was dried over MgSO4 and evaporated under
reduced pressure. The residue was 7.32 g (92%) of
crude compound XVII as a viscous material, Rf 0.48
1
(C6H6–EtOAc, 9:1). H NMR spectrum (acetone-d6),
δ, ppm: 1.80–2.55 m (4H, CH2), 2.29 s (3H, CH3),
2.42 s (3H, CH3), 3.03 s (3H, CH3), 4.82–4.92 m (1H,
CH), 5.69–5.73 m (1H, C=CH), 5.77–5.82 m (1H,
HC=C), 6.95 d (1H, Harom, J = 7.8 Hz), 7.03 d (1H,
(2R,3S,3aR,8bS)-2,3-Epoxy-5,8-dimethyl-4-
methylsulfonyl-1,2,3,3a,4,8b-hexahydrocyclopenta-
[b]indole (XIX). Yield 0.25 g (30%), colorless crys-
Harom, J = 7.8 Hz), 7.75 br.s (NH).
1
Compound XVII was mixed with 13.96 g
(55 mmol) of I2 in 100 ml of methylene chloride and
tals, mp 129–131°C (from EtOH). H NMR spectrum
(C6D6–CCl4), δ, ppm: 1.50 d.d (1H, 1-HA, J1 = 2.0, 2J =
23.18 g (276 mmol) of NaHCO3, and the mixture was
14.0 Hz), 2.10 s (3H, CH3), 2.35 s (3H, CH3), 2.40–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 9 2007

REACTIONS OF N- AND C-ALKENYLANILINES: VIII.
1319
2.55 m (4H, CH3, 1-HB), 3.27 m (1H, 3-H), 3.12 m
(1H, 2-H), 3.20 m (1H, 8b-H), 4.60 d (1H, 3a-H, J =
8.2 Hz), 6.71 d (1H, Harom, J = 7.4 Hz), 6.85 d (1H,
Harom, J = 7.4 Hz). Found, %: C 60.03; H 6.02; N 4.99;
S 11.45. C14H17NO3S. Calculated, %: C 60.19; H 6.13;
N 5.01; S 11.48.
2.10 s (3H, CH3), 2.30 s (3H, CH3), 2.37 d.q.d (1H,
4-Heq, J1 = 2.0, J2 = 3.8, J3 = 13.5 Hz), 2.50 s (3H,
CH3), 2.70 d.d.d (1H, 2-H, J1 = 3.8, J2 = 9.5, J3 =
11.0 Hz), 3.10 d.d (1H, 1-H, J1 = 8.1, J2 = 9.5 Hz),
3.24 d.d.d (1H, 4a-H, J1 = 2.0, J2 = 6.0, J3 = 7.5 Hz),
3.35 s (3H, OCH3), 3.95 d.d (1H, 9a-H, J1 = 7.5, J2 =
9.5 Hz), 6.23 d (1H, Harom, J = 7.7 Hz), 6.93 d (1H,
Harom, J = 7.7 Hz), 7.05 d (2H, Harom, J = 8.0 Hz),
7.45 d (2H, Harom, J = 8.0 Hz). Found, %: C 65.63;
H 6.82; N 3.40; S 7.95. C22H27NO4S. Calculated, %:
C 65.81; H 6.78; N 3.49; S 7.99.
(2S,3R,3aR,8bS)-2,3-Epoxy-5,8-dimethyl-4-
methylsulfonyl-1,2,3,3a,4,8b-hexahydrocyclopenta-
[b]indole (XX). Yield 0.21 g (26%), colorless crystals,
1
mp 147–149°C (from EtOH). H NMR spectrum
(CDCl3), δ, ppm: 2.15–2.30 m (4H, CH3, 1-HA), 2.40–
2.49 m (1H, 1-HB), 2.70 s (3H, CH3), 2.50 s (3H, CH3),
3.55 m (1H, 3-H), 3.84 t (1H, 2-H, J = 2.0 Hz), 4.05 t
(1H, 8b-H, J = 8.7 Hz), 4.95 d.d (1H, 3a-H, J1 = 2.0,
J2 = 8.7 Hz), 6.87 d (1H, Harom, J = 7.7 Hz), 6.98 d
(1H, Harom, J = 7.7 Hz). Found, %: C 60.13; H 6.22;
N 5.05; S 11.45. C14H17NO3S. Calculated, %: C 60.19;
H 6.13; N 5.01; S 11.48.
Reaction of epoxide XIIIa with acetic acid.
A solution of 0.21 g (0.6 mmol) of compound XIIIa,
13 ml of acetic acid, and a catalytic amount of sulfuric
acid was heated for 6 h at 50–60°C. The mixture was
then cooled, 30 ml of methylene chloride and 30 ml of
water were added, and the products were extracted into
methylene chloride (3×25 ml). The extracts were
washed with 10% aqueous NaHCO3 and water (2×
25 ml), dried over MgSO4, and evaporated under
reduced pressure. The residue was recrystallized from
ethanol to isolate diacetate XXIII. The mother liquor
was evaporated under reduced pressure to obtain
0.11 g of crude compound XXII which was purified by
recrystallization from 2 ml of carbon tetrachloride.
Hexahydrocarbazoles XXIa and XXIc (general
procedure). Epoxy derivative XIIIa or XIIIc,
0.6 mmol, was dissolved in 8 ml of benzene, and 20 ml
of methanol and 1 g of KU-2 cation exchanger were
added. The mixture was stirred for 16 h at 40–50°C
and cooled to room temperature, KU-2 was filtered off
and washed with methylene chloride on a filter, the
solvent was distilled off from the filtrate under reduced
pressure, and the residue was recrystallized from
ethanol.
(1S,2S,4aS,9aR)-1-Hydroxy-8-methyl-9-p-tolyl-
sulfonyl-1,2,3,4,4a,9a-hexahydrocarbazol-2-yl ace-
tate (XXII). Yield 0.07 g (27%), colorless crystals,
1
mp 99–101°C. H NMR spectrum (CDCl3), δ, ppm:
(1S,2R,4aS,9aR)-2-Methoxy-8-methyl-9-p-tolyl-
sulfonyl-1,2,3,4,4a,9a-hexahydrocarbazol-1-ol
(XXIa). Yield 0.22 g (96%), colorless crystals,
1.02–2.03 m (4H, CH2); 1.90 br.s (1H, OH); 2.10 s,
2.40 s, and 2.55 s (3H each, CH3); 2.75 m (1H, 4a-H);
3.50 d.d.d (1H, 2-H, J1 = 4.0, J2 = 10.0, J3 = 11.4 Hz);
4.20 d.d (1H, 9a-H, J1 = 6.9, J2 = 9.0 Hz); 4.25 d.d
(1H, 1-H, J1 = 9.0, J2 = 11.4 Hz); 6.80 d (1H, Harom, J =
6.3 Hz); 7.15 d (1H, Harom, J = 6.3 Hz); 7.20 d (2H,
1
mp 157–159°C (from EtOH). H NMR spectrum
(C6D6–CCl4), δ, ppm: 0.80 d.t (1H, 3-Hax, J1 = 3.8, J2 =
13.5 Hz), 1.35 d.t (1H, 4-Hax, J1 = 3.8, J2 = 14.0 Hz),
1.55 d (1H, 3-Heq, J = 13.5 Hz), 1.80 d (1H, 4-Heq, J =
14.0 Hz), 2.20 s (3H, CH3), 2.40 s (3H, CH3), 2.60 m
(1H, 4a-H), 2.75 d.t (1H, 2-H, J1 = 3.8, J2 = 10.0 Hz),
3.00 t (1H, 1-H, J1 = 8.0, J2 = 10.0 Hz), 3.14 s (3H,
CH3), 4.00 t (1H, 9a-H, J1 = 7.4, J2 = 9.5 Hz), 6.55 d
(1H, Harom, J = 7.0 Hz), 6.90 m (4H, Harom), 7.45 d (2H,
H
arom, J = 8.2 Hz); 7.52 d (2H, Harom, J = 8.2 Hz).
13C NMR spectrum (CDCl3), δC, ppm: 19.4, 21.0, 21.5
(CH3); 21.7, 28.2 (CH2); 40.0 (C4a); 69.4, 70.6, 76.4
(C1, C2, C9a); 119.6, 126.9, 127.4, 129.5, 130.7 (C5, C6,
C7, C2′/C6′, C3′/C5′); 134.2, 136.0, 138.2, 140.7, 143.9
(C4b, C8, C8a, C1′, C4′), 171.4 (C=O). Found, %:
C 63.62; H 6.02; N 3.42; S 7.95. C22H25NO5S. Calcu-
lated, %: C 63.59; H 6.06; N 3.37; S 7.72.
Harom, J = 8.0 Hz). Found, %: C 65.02; H 6.42; N 3.59;
S 8.25. C21H25NO4S. Calculated, %: C 65.09; H 6.50;
N 3.61; S 8.28.
(1S,2R,4aS,9aR)-2-Methoxy-5,8-dimethyl-9-
p-tolylsulfonyl-1,2,3,4,4a,9a-hexahydrocarbazol-1-
ol (XXIc). Yield 0.21 g (89%), amorphous material,
(1S,2S,4aS,9aR)-8-Methyl-9-p-tolylsulfonyl-
1,2,3,4,4a,9a-hexahydrocarbazole-1,2-diyl diacetate
(XXIII). Yield 0.13 g (47%), colorless crystals,
1
1
Rf 0.14 (C6H6–EtOAc, 9:1). H NMR spectrum (C6D6–
mp 170–172°C (from EtOH). H NMR spectrum
CCl4), δ, ppm: 1.11 d.d.t (1H, 3-Hax, J1 = 3.8, J2 =
10.0, J = 13.5 Hz), 1.30 s (1H, OH), 1.57 m (1H,
4-Hax), 2.00 q.d (1H, 3-Heq, J1 = 3.8, J2 = 13.5 Hz),
(CDCl3), δ, ppm: 1.10–2.10 m (4H, CH2); 1.95 s,
2.05 s, 2.43 s, and 2.54 s (3H each, CH3); 2.76 t (1H,
4a-H, J = 7.0 Hz); 4.17 d.d (1H, 9a-H, J1 = 7.0, J2 =
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 9 2007

GATAULLIN et al.
1320
7.3 Hz); 4.65 m (2H, 1-H, 2-H); 6.73 d (1H, Harom, J =
1-HB), 1.95 s (3H, CH3), 2.20 s (3H, CH3), 2.50 s (3H,
CH3), 2.78 q (1H, 8b-H, J = 9.0 Hz), 3.20 s (3H,
OCH3), 3.35–3.40 m (1H, 2-H), 4.16 d (1H, 3-H, J =
5.5 Hz), 4.45 d.d (1H, 3a-H, J1 = 5.5, J2 = 9.0 Hz),
6.70 d (1H, Harom, J = 7.5 Hz), 6.89 d (1H, Harom, J =
7.5 Hz), 6.92 d (2H, Harom, J = 8.1 Hz), 7.12 d (2H,
Harom, J = 8.1 Hz). Found, %: C 65.03; H 6.52; N 3.55;
S 8.35. C21H25NO4S. Calculated, %: C 65.09; H 6.50;
N 3.61; S 8.28.
6.0 Hz); 7.10–7.20 m (4H, Harom); 7.52 d (2H, Harom
,
J = 8.3 Hz). 13C NMR spectrum (CDCl3), δC, ppm:
19.3, 20.7, 20.8, 21.5 (CH3); 21.6, 25.2 (CH2); 39.9
(C4a); 69.4, 71.6, 72.3 (C1, C2, C9a); 119.5, 126.9, 130.8
(C6, C7, C8); 127.4, 129.5 (C2′/C6′, C3′/C5′); 134.4,
135.9, 137.9, 140.7, 144.0 (C4b, C8, C8a, C1′, C4′);
170.1, 170.2 (C=O). Found, %: C 63.05; H 6.02;
N 3.09; S 7.10. C24H27NO6S. Calculated, %: C 63.00;
H 5.95; N 3.06; S 7.01.
REFERENCES
Reaction of epoxides XIIIf, XIVd, and XIVf with
methanol (general procedure). Compound XIIIf,
XIVd, or XIVf, 0.4 mmol, was dissolved in 3 ml of
benzene, 13 ml of methanol and 0.6 g of KU-2 cation
exchanger were added, and the mixture was stirred for
6 h at 40–50°C, cooled, and filtered from KU-2, the
precipitate was washed on a filter with methylene chlo-
ride, the filtrate was evaporated under reduced pres-
sure, and the residue was recrystallized from ethanol.
1. Gataullin, R.R., Sotnikov, A.M., Spirikhin, L.V., and
Abdrakhmanov, I.B., Russ. J. Org. Chem., 2005, vol. 41,
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(2S,3S,3aR,8bS)-2-Methoxy-5,8-dimethyl-4-
p-tolylsulfonyl-1,2,3,3a,4,8b-hexahydrocyclopenta-
[b]indol-3-ol (XXIV). Yield 0.14 g (90%), colorless
4. Mustafin, A.G., Khalilov, I.N., Sharafutdinov, V.M.,
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1
crystals, mp 128–130°C (from EtOH). H NMR spec-
trum (C6D6–CCl4), δ, ppm: 1.10–1.22 m (1H, 1-HA),
1.82 s (3H, CH3), 2.07–2.21 m (1H, 1-HB), 2.15 s (3H,
CH3), 2.42 s (3H, CH3), 2.44–2.56 m (1H, 8b-H),
3.18 s (3H, OCH3), 3.33 q (1H, 2-H, J = 8.2 Hz), 3.70 t
(1H, 3-H, J = 7.7 Hz), 4.05 d (1H, 3a-H, J1 = 7.7, J2 =
8.2 Hz), 6.65 d (1H, Harom, J = 7.6 Hz), 6.80–6.90 d
(3H, Harom), 7.15 d (2H, Harom, J = 8.2 Hz). Found, %:
C 64.93; H 6.62; N 3.59; S 8.35. C21H25NO4S. Calcu-
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(2R,3R,3aR,8bS)-2-Methoxy-5-methyl-4-p-tolyl-
sulfonyl-1,2,3,3a,4,8b-hexahydrocyclopenta[b]indol-
3-ol (XXVd). Yield 0.14 g (74%), amorphous material,
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1
Rf 0.21 (C6H6–EtOAc, 9:1). H NMR spectrum
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(C6D6), δ, ppm: 1.55–2.00 m (2H, CH2); 2.20 s, 2.55 s,
and 3.20 s (3H each, CH3); 2.70 q (1H, 8b-H, J =
9.0 Hz); 3.15 m (1H, 2-H); 4.09 d.d (1H, 3-H, J1 = 3.6,
J2 = 6.3 Hz); 4.48 d.d (1H, 3a-H, J1 = 6.3, J2 = 8.1 Hz);
6.65 d (1H, Harom, J = 7.3 Hz); 6.90–7.10 m (4H,
Harom); 7.20 d (2H, Harom, J = 8.2 Hz). Found, %:
C 64.63; H 6.02; N 3.79; S 8.55. C20H23NO4S. Calcu-
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1
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(1H, 1-HA, J1 = 6.0, J2 = 12.0 Hz), 1.90–2.10 m (1H,
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